KR20230026531A - Low-friction film, manufacturing method therefor, molded body, and method for enhancing finger slipperiness - Google Patents
Low-friction film, manufacturing method therefor, molded body, and method for enhancing finger slipperiness Download PDFInfo
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- KR20230026531A KR20230026531A KR1020237004881A KR20237004881A KR20230026531A KR 20230026531 A KR20230026531 A KR 20230026531A KR 1020237004881 A KR1020237004881 A KR 1020237004881A KR 20237004881 A KR20237004881 A KR 20237004881A KR 20230026531 A KR20230026531 A KR 20230026531A
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- friction
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Classifications
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Abstract
적어도 한쪽 표면의 첨도(Rku)가 2 이상이며, 또한 상기 표면의 최대 단면 높이(Rt)가 1㎛ 이상인 필름을 조제한다. 상기 표면의 동마찰 계수는 0.25 이하여도 되고, 상대 동마찰 계수는 0.3 이하여도 된다. 상기 필름은, 경화성 수지를 포함하는 경화성 조성물의 경화물로 형성된 저마찰층을 포함하고, 또한 이 저마찰층의 표면이 상기 범위의 Rku 및 Rt를 갖고 있어도 된다. 상기 경화성 수지는, 중합성기를 갖는 (메트)아크릴계 중합체, 우레탄(메트)아크릴레이트 및 실리콘(메트)아크릴레이트로 이루어지는 군에서 선택된 적어도 1종을 포함하고 있어도 된다. 상기 경화성 조성물은 셀룰로오스에스테르를 더 포함하고 있어도 된다. 상기 경화성 조성물은 미립자를 포함하지 않아도 된다. 이 필름은, 폭넓은 종류의 재질로 표면을 형성하더라도, 동마찰 계수를 저감할 수 있다.A film having a kurtosis (Rku) of at least one surface of 2 or more and a maximum section height (Rt) of the surface of 1 μm or more is prepared. The coefficient of kinetic friction of the surface may be 0.25 or less, and the coefficient of relative kinetic friction may be 0.3 or less. The film may include a low-friction layer formed of a cured product of a curable composition containing a curable resin, and the surface of the low-friction layer may have Rku and Rt within the above ranges. The said curable resin may contain at least 1 sort(s) selected from the group which consists of a (meth)acrylic-type polymer, urethane (meth)acrylate, and silicone (meth)acrylate which have a polymeric group. The curable composition may further contain a cellulose ester. The curable composition may not contain fine particles. This film can reduce the coefficient of kinetic friction even when the surface is formed with a wide variety of materials.
Description
본 발명은 터치 패널 디스플레이, 가전 제품의 하우징, 건축 재료 등의 각종 성형체의 표면을 커버하기 위한 저마찰 필름 및 그의 제조 방법, 성형체 그리고 이 필름의 미끄럼성(특히, 손가락 미끄럼성) 향상 방법에 관한 것이다.The present invention relates to a low-friction film for covering surfaces of various molded bodies such as touch panel displays, home appliance housings, building materials, and the like, a method for manufacturing the same, a molded body, and a method for improving the slipperiness (particularly, finger slipperiness) of the film. will be.
퍼스널 컴퓨터(PC)나 스마트폰 등에 있어서의 터치 패널 디스플레이, 가전 제품의 하우징, 건축 재료 등의 각종 성형체의 표면에는, 흠집이 나는 것을 방지하기 위해서나, 닿는 느낌을 향상시키기 위해서, 표면 보호층 또는 커버층으로서, 하드 코트 필름을 붙이는 방법이나 하드 코트 처리를 실시하는 방법이 알려져 있다. 이 하드 코트 필름이나 하드 코트층에는, 손으로 접촉했을 때의 미끄럼이 좋을 것이 요구되는데, 미끄럼성의 향상 방법으로서는, 종래부터, 실리콘 화합물이나 불소 화합물을 포함하는 하드 코트 처리를 실시함으로써 미끄럼성을 향상시키는 것이 일반적이다.Surface protective layer or cover to prevent scratches on the surface of various molded objects such as touch panel displays in personal computers (PCs) and smartphones, housings of household appliances, and building materials, or to improve the touch feeling As a layer, a method of attaching a hard coat film or a method of performing a hard coat treatment is known. The hard coat film and the hard coat layer are required to have good slippage when touched by hand, but as a method for improving the slipperiness, conventionally, the slipperiness is improved by performing a hard coat treatment containing a silicone compound or a fluorine compound. It is common to do
일본 특허 공개 제2007-264281호 공보(특허문헌 1)에는, 광학 적층체에 사용되는 하드 코트층이며, 방오염제 및/또는 미끄럼성 부여제로서, 규소계 화합물, 불소계 화합물 또는 이들의 혼합물을 포함하여 이루어지고, 상기 하드 코트층의 최표면을 XPS 해석한 경우에, 규소 원자의 존재율이 10% 이상이고/이거나 불소 원자의 존재율이 20% 이상인 하드 코트층이 개시되어 있다.In Japanese Unexamined Patent Publication No. 2007-264281 (Patent Document 1), it is a hard coat layer used for an optical laminate, and a silicon-based compound, a fluorine-based compound, or a mixture thereof is used as an antifouling agent and/or a slippery imparting agent. A hard coat layer is disclosed in which the abundance of silicon atoms is 10% or more and/or the abundance of fluorine atoms is 20% or more, in the case of XPS analysis of the outermost surface of the hard coat layer.
또한, WO2008/038714(특허문헌 2)에는, 기재와, 이 기재 상에 형성된 광학 기능층과, 상기 광학 기능층 상에 형성되고, 표면의 원소 비율이 규소 원소(Si)와 탄소 원소(C)의 비 Si/C가 0.25 내지 1이며, 불소 원소(F)와 탄소 원소(C)의 비 F/C가 0.1 내지 1이며, 유동 파라핀 접촉각 및 전락각이 65° 이상 및 15° 이하이고, 흑색 매직 접촉각 및 전락각이 35° 이상 및 15° 이하이고, 또한 동마찰 계수가 0.15 미만인 방오층을 갖는 광학 기능 필름이 개시되어 있다.Further, in WO2008/038714 (Patent Document 2), a base material, an optical function layer formed on the base material, and a surface element ratio formed on the optical function layer are silicon element (Si) and carbon element (C) The ratio of Si / C is 0.25 to 1, the ratio F / C of fluorine element (F) to carbon element (C) is 0.1 to 1, the liquid paraffin contact angle and sliding angle are 65 ° or more and 15 ° or less, black An optical function film having an antifouling layer having a magic contact angle and a sliding angle of 35° or more and 15° or less, and a kinetic friction coefficient of less than 0.15 is disclosed.
그러나, 이들 하드 코트층 및 방오층에서는, 실리콘 화합물이나 불소 화합물에 의해 표면의 마찰 계수를 저감할 수 있지만, 충분하지 않은 데다가 표면 구조의 미세한 차이에 의해, 손가락 미끄럼성은 크게 상이했다. 또한, 표면이 발수성이 되기 때문에, 용도가 제한되는 데다가 습식 코팅에 의해 표면을 레벨링하기 때문에, 대류 현상을 이용하여 표면 형상을 제어하는 것이 곤란하다.However, in these hard coat layers and antifouling layers, although the friction coefficient of the surface can be reduced by silicone compounds or fluorine compounds, it is not sufficient, and the finger slipperiness is greatly different due to minute differences in surface structures. In addition, since the surface becomes water repellent, its application is limited, and since the surface is leveled by wet coating, it is difficult to control the surface shape using convection.
따라서, 본 발명의 목적은, 폭넓은 종류의 재질로 표면을 형성하더라도, 동마찰 계수를 저감할 수 있는 저마찰 필름, 성형체 및 그의 제조 방법 그리고 이 필름의 손가락 미끄럼성 향상 방법을 제공하는 데 있다.Accordingly, an object of the present invention is to provide a low-friction film capable of reducing the coefficient of kinetic friction even when the surface is formed of a wide variety of materials, a molded article, a method for manufacturing the same, and a method for improving finger slippage of the film. .
또한, 본 발명의 다른 목적은, 다량의 실리콘 화합물이나 불소 화합물을 배합하지 않고, 미끄럼성(특히, 손가락 미끄럼성)을 향상시킬 수 있는 저마찰 필름 및 그의 제조 방법, 성형체 그리고 이 필름의 미끄럼성(특히, 손가락 미끄럼성) 향상 방법을 제공하는 데 있다.Another object of the present invention is a low-friction film capable of improving slipperiness (particularly, finger slipperiness) without blending a large amount of silicone compound or fluorine compound, a method for producing the same, a molded article, and the slipperiness of the film It is to provide a method for improving (particularly, finger slipperiness).
본 발명자는, 상기 과제를 달성하기 위하여 예의 검토한 결과, 필름 표면의 첨도(Rku) 및 최대 단면 높이(Rt)를 조정함으로써, 폭넓은 종류의 재질로 표면을 형성하더라도, 동마찰 계수를 저감할 수 있음을 알아내고, 본 발명을 완성하였다.As a result of intensive studies to achieve the above object, the inventors of the present invention, by adjusting the kurtosis (Rku) and the maximum section height (Rt) of the film surface, even if the surface is formed with a wide variety of materials, the kinetic friction coefficient can be reduced It was found that it could be done, and the present invention was completed.
즉, 본 발명의 필름(저마찰 필름)은 적어도 한쪽 표면이 2 이상의 Rku 및 1㎛ 이상의 Rt를 갖는다. 상기 표면의 동마찰 계수는 0.25 이하여도 되고, 상대 동마찰 계수는 0.3 이하여도 된다. 상기 필름은, 경화성 수지를 포함하는 경화성 조성물의 경화물로 형성되고, 또한 최표층에 배치된 저마찰층을 포함하고, 또한 이 저마찰층의 표면이 2 이상의 Rku 및 1㎛ 이상의 Rt를 갖고 있어도 된다. 상기 경화성 수지는, 중합성기를 갖는 (메트)아크릴계 중합체, 우레탄(메트)아크릴레이트 및 실리콘(메트)아크릴레이트로 이루어지는 군에서 선택된 적어도 1종을 포함하고 있어도 된다. 상기 경화성 조성물은 셀룰로오스에스테르를 더 포함하고 있어도 된다. 상기 경화성 조성물은 미립자를 포함하지 않아도 된다. 상기 저마찰 필름은, 투명 수지로 형성된 기재층 상에 저마찰층이 적층되어 있어도 된다. 상기 필름은, 표면의 규소 원자의 존재율이 10% 미만이고, 또한 표면의 불소 원자의 존재율이 20% 미만이어도 된다.That is, the film (low-friction film) of the present invention has Rku of 2 or more and Rt of 1 μm or more on at least one surface. The coefficient of kinetic friction of the surface may be 0.25 or less, and the coefficient of relative kinetic friction may be 0.3 or less. Even if the film is formed of a cured product of a curable composition containing a curable resin and includes a low-friction layer disposed on an outermost layer, and the surface of the low-friction layer has an Rku of 2 or more and an Rt of 1 μm or more. do. The said curable resin may contain at least 1 sort(s) selected from the group which consists of a (meth)acrylic-type polymer, urethane (meth)acrylate, and silicone (meth)acrylate which have a polymeric group. The curable composition may further contain a cellulose ester. The curable composition may not contain fine particles. In the low-friction film, a low-friction layer may be laminated on a substrate layer formed of a transparent resin. In the film, the presence rate of silicon atoms on the surface is less than 10%, and the abundance rate of fluorine atoms on the surface may be less than 20%.
본 발명에는, 경화성 수지를 포함하는 경화성 조성물을 경화하는 경화 공정을 포함하는 상기 필름의 제조 방법도 포함된다. 또한, 본 발명에는, 표면에 상기 필름을 구비한 성형체도 포함된다. 이 성형체는, 터치 패널 디스플레이여도 된다. 또한, 본 발명에는, 필름의 적어도 한쪽 표면을, 2 이상의 첨도(Rku) 및 1㎛ 이상의 최대 단면 높이(Rt)로 조정함으로써, 필름의 손가락 미끄럼성을 향상시키는 방법도 포함된다.The manufacturing method of the said film which includes the hardening process of hardening the curable composition containing curable resin is also included in this invention. Moreover, the molded object which provided the said film on the surface is also contained in this invention. A touch panel display may be sufficient as this molded object. Moreover, the method of improving the finger slipperiness of a film is also included in this invention by adjusting at least one surface of a film to a kurtosis (Rku) of 2 or more, and a maximum section height (Rt) of 1 micrometer or more.
본 발명에서는, 필름 표면의 요철 구조에 있어서 Rku 및 Rt가 특정한 범위로 조정되어 있기 때문에, 폭넓은 종류의 재질로 필름 표면을 형성하더라도, 동마찰 계수를 저감할 수 있다. 그 때문에, 다량의 실리콘 화합물이나 불소 화합물을 배합하지 않고, 필름의 미끄럼성(특히, 손가락 미끄럼성 또는 닿는 느낌)을 향상시킬 수 있다.In the present invention, since Rku and Rt are adjusted to a specific range in the concavo-convex structure of the film surface, the coefficient of kinetic friction can be reduced even if the film surface is formed with a wide variety of materials. Therefore, the slipperiness of the film (particularly, finger slipperiness or touch feeling) can be improved without blending a large amount of a silicone compound or a fluorine compound.
[저마찰 필름][Low friction film]
본 발명의 필름(저마찰 필름)은, 적어도 한쪽 표면의 Rku(첨도)가 2 이상이며, 또한 상기 표면의 Rt가 1㎛ 이상으로 조정되어 있기 때문에, 첨도 및 고저차가 큰 볼록부가 표면에 형성되어 있다. 그 때문에, 본 발명의 저마찰 필름에서는, 표면이 손가락 등의 피접촉체와 접촉하는 경우, 접촉 면적이 작기 때문에, 동마찰 계수를 저감할 수 있다고 추정할 수 있다. Rku 및 Rt가 상기 범위로 조정된 요철 구조를 갖는 표면은, 양면에 형성되어 있어도 되지만, 통상, 손가락과 접촉하는 측이 되는 편면에 형성되어 있는 경우가 많다.In the film (low-friction film) of the present invention, since Rku (kurtosis) of at least one surface is 2 or more and Rt of the surface is adjusted to 1 μm or more, convex portions with large kurtosis and height difference are formed on the surface, there is. Therefore, in the low-friction film of the present invention, when the surface comes into contact with a to-be-contacted object such as a finger, it can be estimated that the kinetic friction coefficient can be reduced because the contact area is small. Although the surface having the concavo-convex structure in which Rku and Rt are adjusted to the above ranges may be formed on both surfaces, it is often formed on one side that is usually in contact with a finger.
상기 표면의 Rku(첨도)는 2 이상(예를 들어 2 내지 100)이면 되고, 예를 들어 2.5 내지 80(예를 들어 3 내지 50), 바람직하게는 3.2 내지 30(예를 들어 3.3 내지 20), 더욱 바람직하게는 3.5 내지 10(특히 4 내지 5) 정도이다. Rku가 너무 작으면, 표면의 동마찰 계수를 저감할 수 없어, 손가락 미끄럼성을 향상시킬 수 없다.Rku (kurtosis) of the surface may be 2 or more (eg 2 to 100), eg 2.5 to 80 (eg 3 to 50), preferably 3.2 to 30 (eg 3.3 to 20). , more preferably about 3.5 to 10 (particularly 4 to 5). If Rku is too small, the coefficient of kinetic friction of the surface cannot be reduced and the finger slipperiness cannot be improved.
상기 표면의 Rt(최대 단면 높이)는 1㎛ 이상(예를 들어 1 내지 30㎛)이면 되고, 예를 들어 1.5 내지 20㎛(예를 들어 2 내지 15㎛), 바람직하게는 2 내지 10㎛(예를 들어 2.5 내지 8㎛), 더욱 바람직하게는 3 내지 5㎛(특히 3.5 내지 4.5㎛) 정도이다. Rt가 너무 작으면, 표면의 동마찰 계수를 저감할 수 없어, 손가락 미끄럼성을 향상시킬 수 없다.The Rt (maximum cross-sectional height) of the surface may be 1 μm or more (for example, 1 to 30 μm), for example, 1.5 to 20 μm (for example, 2 to 15 μm), preferably 2 to 10 μm ( For example, about 2.5 to 8 μm), more preferably about 3 to 5 μm (especially about 3.5 to 4.5 μm). If Rt is too small, the coefficient of kinetic friction of the surface cannot be reduced and the finger slipperiness cannot be improved.
부언하면, 본 명세서 및 특허 청구 범위에 있어서, Rku 및 Rt는, JIS B0601에 준거하여, 광학식 표면 조도계 등을 사용하여 측정할 수 있고, 상세하게는, 후술하는 실시예에 기재된 방법으로 측정할 수 있다.Incidentally, in the present specification and claims, Rku and Rt can be measured using an optical surface roughness meter or the like in accordance with JIS B0601, and in detail, can be measured by the method described in Examples to be described later. there is.
상기 표면은, Rku 및 Rt가 상기 범위로 조정된 요철 구조를 갖고 있기 때문에, 동마찰 계수(μk)가 낮으며, 상기 표면의 동마찰 계수는 0.25 이하여도 되고, 예를 들어 0.01 내지 0.23, 바람직하게는 0.03 내지 0.2, 더욱 바람직하게는 0.05 내지 0.15(특히 0.08 내지 0.12) 정도이다. 또한, 상대 동마찰 계수는 0.3 이하여도 되고, 예를 들어 0.01 내지 0.29, 바람직하게는 0.04 내지 0.25, 더욱 바람직하게는 0.06 내지 0.19(특히 0.1 내지 0.15) 정도여도 된다.Since the surface has a concavo-convex structure in which Rku and Rt are adjusted to the above ranges, the kinetic friction coefficient (μk) is low, and the kinetic friction coefficient of the surface may be 0.25 or less, for example, 0.01 to 0.23, preferably 0.01 to 0.23. Preferably it is about 0.03 to 0.2, more preferably about 0.05 to 0.15 (particularly about 0.08 to 0.12). The coefficient of relative kinetic friction may be 0.3 or less, for example, 0.01 to 0.29, preferably 0.04 to 0.25, and more preferably 0.06 to 0.19 (particularly 0.1 to 0.15).
부언하면, 본 명세서 및 특허 청구 범위에 있어서, 동마찰력은, 정동 마찰 측정기를 사용하여 측정할 수 있고, 상세하게는, 후술하는 실시예에 기재된 방법으로 측정할 수 있다. 한편, 상대 동마찰 계수는, 동일한 하중으로 측정한 필름의 동마찰력을, 유리를 검체로 하여 측정한 동마찰력으로 나눈 값이며, 상세하게는, 후술하는 실시예에 기재된 방법으로 측정할 수 있다. 이 상대 동마찰 계수는, 안정된 유리 표면의 동마찰력과의 상대값으로서, 필름의 마찰 특성을 평가하고 있기 때문에, 인공 피부의 경시 변화에 따른 오차를 완화한 신뢰성이 높은 평가이다.Incidentally, in the present specification and claims, the kinetic frictional force can be measured using a static friction measuring instrument, and in detail, can be measured by the method described in Examples to be described later. On the other hand, the relative kinetic friction coefficient is a value obtained by dividing the kinetic frictional force of a film measured under the same load by the kinetic frictional force measured using glass as a sample, and can be measured in detail by the method described in Examples described later. This relative kinetic friction coefficient is a relative value with the kinetic frictional force of the stable glass surface, and since the frictional properties of the film are evaluated, it is a highly reliable evaluation in which errors due to changes in artificial skin over time are mitigated.
본 발명의 저마찰 필름은, 적어도 한쪽 표면의 Rku 및 Rt가 상기 범위로 조정된 요철 구조를 갖고 있으면 되고, 필름의 재질이나 구조는, 특별히 한정되지 않는다.The low-friction film of the present invention should have a concavo-convex structure in which Rku and Rt on at least one surface are adjusted to the above ranges, and the material and structure of the film are not particularly limited.
재질에 대해서, 본 발명의 저마찰 필름은, 표면의 Rku 및 Rt가 상기 범위로 조정되어 있기 때문에, 실리콘 화합물 및 불소 화합물을 다량으로 포함하고 있지 않아도, 동마찰 계수를 저감할 수 있다. 그 때문에, 저마찰 필름 표면(특히, 상기 범위의 Rku 및 Rt를 갖는 표면)의 규소 원자의 존재율은 10% 미만이어도 되고, 바람직하게는 5% 이하, 더욱 바람직하게는 1% 이하여도 된다. 또한, 저마찰 필름 표면(특히, 상기 범위의 Rku 및 Rt를 갖는 표면)의 불소 원자의 존재율은 20% 미만이어도 되고, 바람직하게는 10% 이하, 더욱 바람직하게는 1% 이하여도 된다. 부언하면, 본 명세서 및 특허 청구 범위에 있어서, 규소 원자 및 불소 원자의 존재율은, X선 광전자 분광 장치(XPS)를 사용한 관용의 방법으로 측정할 수 있다.Regarding the material, since Rku and Rt of the surface of the low-friction film of the present invention are adjusted to the above ranges, the coefficient of kinetic friction can be reduced even without containing a large amount of a silicone compound or a fluorine compound. Therefore, the abundance of silicon atoms on the surface of the low-friction film (particularly, the surface having Rku and Rt within the above ranges) may be less than 10%, preferably 5% or less, and more preferably 1% or less. Further, the abundance of fluorine atoms on the surface of the low-friction film (particularly, the surface having Rku and Rt within the above ranges) may be less than 20%, preferably 10% or less, and more preferably 1% or less. Incidentally, in the present specification and claims, the abundance of silicon atoms and fluorine atoms can be measured by a conventional method using an X-ray photoelectron spectroscopy (XPS).
구조에 대해서, 본 발명의 저마찰 필름은, 예를 들어, 적어도 한쪽 표면의 Rku 및 Rt가 상기 범위로 조정되어 있는 단층 필름이어도 되고, 표면의 Rku 및 Rt가 상기 범위로 조정되어 있는 저마찰층을 포함하는 적층체여도 된다.Regarding the structure, the low-friction film of the present invention may be, for example, a single layer film in which Rku and Rt of at least one surface are adjusted to the above ranges, or a low-friction layer in which Rku and Rt of the surface are adjusted to the above ranges. It may be a laminate containing.
(단층 필름 및 저마찰층)(Single-layer film and low-friction layer)
단층 필름 및 저마찰층의 재질은, 전술한 바와 같이 한정되지 않고, 각종 유기 재료(열가소성 수지, 열경화성 수지, 광경화성 수지 등)나 무기 재료(유리, 세라믹스, 금속 등)로부터 선택할 수 있지만, 생산성 등의 점에서, 경화성 수지를 포함하는 경화성 조성물의 경화물이 바람직하다.The material of the single-layer film and the low-friction layer is not limited as described above, and can be selected from various organic materials (thermoplastic resin, thermosetting resin, photocurable resin, etc.) or inorganic material (glass, ceramics, metal, etc.). From these points, a cured product of a curable composition containing a curable resin is preferred.
경화성 수지는, 열경화성 수지, 광경화성 수지 중 어느 것이어도 되지만, 생산성 등의 점에서, (메트)아크릴계 광경화성 수지가 범용된다. 또한, (메트)아크릴계 수지는, 투명성도 우수하기 때문에, 터치 패널 디스플레이 등의 광학 용도의 보호 필름으로서 적합하게 이용할 수 있다.The curable resin may be any of a thermosetting resin and a photocurable resin, but (meth)acrylic photocurable resins are generally used in terms of productivity and the like. Moreover, since (meth)acrylic-type resin is excellent also in transparency, it can be used suitably as a protective film for optical applications, such as a touch panel display.
(메트)아크릴계 광경화성 수지로서는, 예를 들어, 다관능성 (메트)아크릴레이트[예를 들어, 펜타에리트리톨테트라(메트)아크릴레이트, 디펜타에리트리톨펜타(메트)아크릴레이트, 디펜타에리트리톨헥사(메트)아크릴레이트 등의 2 내지 8 정도의 중합성기를 갖는 (메트)아크릴레이트 등], 에폭시(메트)아크릴레이트[2 이상의 (메트)아크릴로일기를 갖는 다관능성 에폭시(메트)아크릴레이트], 폴리에스테르(메트)아크릴레이트[2 이상의 (메트)아크릴로일기를 갖는 다관능성 폴리에스테르(메트)아크릴레이트], 우레탄(메트)아크릴레이트[2 이상의 (메트)아크릴로일기를 갖는 다관능성 우레탄(메트)아크릴레이트], 실리콘(메트)아크릴레이트[2 이상의 (메트)아크릴로일기를 갖는 다관능성 실리콘(메트)아크릴레이트], 중합성기를 갖는 (메트)아크릴계 중합체 등을 들 수 있다. 이들 경화성 수지는, 단독으로 또는 2종 이상 조합하여 사용할 수 있다.Examples of the (meth)acrylic photocurable resin include polyfunctional (meth)acrylates [eg, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol (meth)acrylates having about 2 to 8 polymerizable groups such as hexa(meth)acrylate, etc.], epoxy (meth)acrylates [polyfunctional epoxy (meth)acrylates having two or more (meth)acryloyl groups ], polyester (meth) acrylate [polyfunctional polyester (meth) acrylate having two or more (meth) acryloyl groups], urethane (meth) acrylate [polyfunctional having two or more (meth) acryloyl groups] urethane (meth)acrylate], silicone (meth)acrylate [polyfunctional silicone (meth)acrylate having two or more (meth)acryloyl groups], (meth)acrylic polymer having a polymerizable group, and the like. These curable resins can be used individually or in combination of 2 or more types.
이들 경화성 수지 중, 우레탄(메트)아크릴레이트, 실리콘(메트)아크릴레이트, 중합성기를 갖는 (메트)아크릴계 중합체가 바람직하고, 중합성기를 갖는 (메트)아크릴계 중합체가 특히 바람직하다. 중합성기를 갖는 (메트)아크릴계 중합체는, (메트)아크릴계 중합체의 카르복실기의 일부에 중합성 불포화기를 도입한 중합체, 예를 들어, (메트)아크릴산-(메트)아크릴산에스테르 공중합체의 카르복실기의 일부에, 에폭시기 함유 (메트)아크릴레이트(예를 들어, 3,4-에폭시시클로헥세닐메틸아크릴레이트 등)의 에폭시기를 반응시켜서, 측쇄에 중합성기(광중합성 불포화기)를 도입한 (메트)아크릴계 중합체(다이셀·올넥스(주)제 「사이클로머 P」)여도 된다.Among these curable resins, urethane (meth)acrylate, silicone (meth)acrylate, and (meth)acrylic polymers having a polymerizable group are preferred, and (meth)acrylic polymers having a polymerizable group are particularly preferred. The (meth)acrylic polymer having a polymerizable group is a polymer in which a polymerizable unsaturated group is introduced into a part of the carboxyl group of the (meth)acrylic polymer, for example, a part of the carboxyl group of a (meth)acrylic acid-(meth)acrylic acid ester copolymer. , (meth)acrylic polymer obtained by reacting the epoxy group of an epoxy group-containing (meth)acrylate (for example, 3,4-epoxycyclohexenylmethyl acrylate, etc.) to introduce a polymerizable group (photopolymerizable unsaturated group) into the side chain (“Cyclomer P” manufactured by Daicel Allnex Co., Ltd.) may be used.
중합성기를 갖는 (메트)아크릴계 중합체는, 우레탄(메트)아크릴레이트 및/또는 실리콘(메트)아크릴레이트와 조합하는 것이 바람직하고, 우레탄(메트)아크릴레이트 및 실리콘(메트)아크릴레이트와 조합하는 것이 특히 바람직하다.The (meth)acrylic polymer having a polymerizable group is preferably combined with urethane (meth)acrylate and/or silicone (meth)acrylate, and is preferably combined with urethane (meth)acrylate and silicone (meth)acrylate. particularly preferred.
중합성기를 갖는 (메트)아크릴계 중합체와, 우레탄(메트)아크릴레이트 및/또는 실리콘(메트)아크릴레이트를 조합하는 경우, 우레탄(메트)아크릴레이트의 비율은, 중합성기를 갖는 (메트)아크릴계 중합체 100중량부에 대하여 예를 들어 10 내지 300중량부, 바람직하게는 100 내지 200중량부, 더욱 바람직하게는 120 내지 180중량부 정도이다. 실리콘(메트)아크릴레이트의 비율은, 중합성기를 갖는 (메트)아크릴계 중합체 100중량부에 대하여 예를 들어 0.1 내지 10중량부, 바람직하게는 0.5 내지 5중량부, 더욱 바람직하게는 1 내지 3중량부 정도이다.When a (meth)acrylic polymer having a polymerizable group and urethane (meth)acrylate and/or silicone (meth)acrylate are combined, the ratio of urethane (meth)acrylate is the (meth)acrylic polymer having a polymerizable group For 100 parts by weight, it is, for example, about 10 to 300 parts by weight, preferably about 100 to 200 parts by weight, and more preferably about 120 to 180 parts by weight. The proportion of silicone (meth)acrylate is, for example, 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight, based on 100 parts by weight of the (meth)acrylic polymer having a polymerizable group. It is about wealth.
경화성 조성물은, 상기 경화성 수지에 추가로, 셀룰로오스에스테르를 더 포함하고 있어도 된다. 셀룰로오스에스테르로서는, 예를 들어, 셀룰로오스디아세테이트, 셀룰로오스트리아세테이트 등의 셀룰로오스아세테이트; 셀룰로오스프로피오네이트, 셀룰로오스부티레이트, 셀룰로오스아세테이트프로피오네이트, 셀룰로오스아세테이트부티레이트 등의 셀룰로오스 C2-6 아실레이트 등을 들 수 있다. 이들 셀룰로오스에스테르는, 단독으로 또는 2종 이상 조합하여 사용할 수 있다. 이들 중, 셀룰로오스디아세테이트, 셀룰로오스트리아세테이트, 셀룰로오스아세테이트프로피오네이트, 셀룰로오스아세테이트부티레이트 등의 셀룰로오스 C2-4 아실레이트가 바람직하고, 셀룰로오스아세테이트프로피오네이트 등의 셀룰로오스아세테이트 C3-4 아실레이트가 특히 바람직하다. 셀룰로오스에스테르의 비율은, 경화성 수지 100중량부에 대하여 예를 들어 0.1 내지 30중량부, 바람직하게는 0.5 내지 20중량부, 더욱 바람직하게는 1 내지 10중량부(특히 2 내지 5중량부) 정도이다.The curable composition may further contain a cellulose ester in addition to the curable resin. Examples of the cellulose ester include cellulose acetates such as cellulose diacetate and cellulose triacetate; and cellulose C 2-6 acylates such as cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate. These cellulose esters can be used individually or in combination of 2 or more types. Among these, cellulose C 2-4 acylates such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate and cellulose acetate butyrate are preferred, and cellulose acetate C 3-4 acylates such as cellulose acetate propionate are particularly preferred. desirable. The proportion of the cellulose ester is, for example, 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight (particularly 2 to 5 parts by weight) with respect to 100 parts by weight of the curable resin. .
경화성 조성물은, 상기 경화성 수지에 추가로, 미립자를 더 포함하고 있어도 된다. 미립자로서는, 예를 들어, 실리카 입자, 티타니아 입자, 지르코니아 입자, 알루미나 입자 등의 무기 미립자, (메트)아크릴계 단량체와 스티렌계 단량체의 공중합체 입자, 가교 (메트)아크릴계 중합체 입자, 가교 스티렌계 수지 입자 등의 유기 미립자 등을 들 수 있다. 이들 미립자는, 단독으로 또는 2종 이상 조합하여 사용할 수 있다. 이들 중, 가교 (메트)아크릴계 중합체 입자 등이 범용된다. 미립자의 평균 입경은, 예를 들어 1 내지 30㎛, 바람직하게는 10 내지 30㎛, 더욱 바람직하게는 15 내지 25㎛ 정도이다. 미립자의 비율은, 경화성 수지 100중량부에 대하여 예를 들어 0.1 내지 10중량부, 바람직하게는 0.2 내지 5중량부, 더욱 바람직하게는 0.3 내지 3중량부(특히 0.4 내지 1중량부) 정도이다.The curable composition may further contain fine particles in addition to the curable resin. Examples of the fine particles include inorganic fine particles such as silica particles, titania particles, zirconia particles, and alumina particles, copolymer particles of a (meth)acrylic monomer and a styrenic monomer, crosslinked (meth)acrylic polymer particles, and crosslinked styrenic resin particles. Organic particulates, such as these, etc. are mentioned. These microparticles|fine-particles can be used individually or in combination of 2 or more types. Among these, crosslinked (meth)acrylic polymer particles and the like are generally used. The average particle diameter of the fine particles is, for example, about 1 to 30 μm, preferably about 10 to 30 μm, and more preferably about 15 to 25 μm. The proportion of fine particles is, for example, 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0.3 to 3 parts by weight (particularly 0.4 to 1 part by weight), based on 100 parts by weight of the curable resin.
부언하면, 본 발명에서는, 경화성 수지[특히, 중합성기를 갖는 (메트)아크릴계 중합체와, 우레탄(메트)아크릴레이트 및/또는 실리콘(메트)아크릴레이트의 조합]와, 셀룰로오스에스테르를 조합하는 경우, 미립자를 사용하지 않고, 상기 범위의 Rku 및 Rt를 갖고, 또한 동마찰 계수가 낮은 표면을 형성할 수 있다.Incidentally, in the present invention, when combining a curable resin [particularly, a combination of a (meth)acrylic polymer having a polymerizable group, urethane (meth)acrylate and/or silicone (meth)acrylate] and a cellulose ester, A surface having Rku and Rt within the above ranges and having a low coefficient of kinetic friction can be formed without using fine particles.
경화성 조성물은, 상기 경화성 수지에 추가로, 관용의 첨가제, 예를 들어, 중합 개시제, 안정제(산화 방지제, 자외선 흡수제 등), 계면 활성제, 수용성 고분자, 충전제, 가교제, 커플링제, 착색제, 난연제, 활제, 왁스, 방부제, 점도 조정제, 증점제, 레벨링제, 소포제 등이 포함되어 있어도 된다. 이들 첨가제는, 단독으로 또는 2종 이상 조합하여 사용할 수 있다.The curable composition, in addition to the curable resin, conventional additives such as polymerization initiators, stabilizers (antioxidants, ultraviolet absorbers, etc.), surfactants, water-soluble polymers, fillers, crosslinking agents, coupling agents, colorants, flame retardants, lubricants , wax, antiseptic agent, viscosity modifier, thickener, leveling agent, antifoaming agent and the like may be contained. These additives can be used individually or in combination of 2 or more types.
경화성 조성물이 광경화성 조성물일 경우, 광경화성 조성물은, 중합 개시제로서, 광중합 개시제를 포함하고 있어도 된다. 광중합 개시제로서는, 예를 들어, 아세토페논류 또는 프로피오페논류, 벤질류, 벤조인류, 벤조페논류, 티오크산톤류, 아실포스핀옥시드류 등을 예시할 수 있다. 광중합 개시제에는, 관용의 광증감제나 광중합 촉진제(예를 들어, 제3급 아민류 등)가 포함되어 있어도 된다. 광중합 개시제의 비율은, 광경화성 수지 100중량부에 대하여 예를 들어 0.1 내지 10중량부, 바람직하게는 0.5 내지 5중량부, 더욱 바람직하게는 1 내지 3중량부 정도이다.When the curable composition is a photocurable composition, the photocurable composition may contain a photopolymerization initiator as a polymerization initiator. As a photoinitiator, acetophenones or propiophenones, benzyls, benzoins, benzophenones, thioxanthones, acylphosphine oxides etc. can be illustrated, for example. The photopolymerization initiator may contain a conventional photosensitizer or photopolymerization accelerator (eg, tertiary amines). The ratio of the photopolymerization initiator is, for example, 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, and more preferably about 1 to 3 parts by weight, based on 100 parts by weight of the photocurable resin.
경화 전의 경화성 조성물은, 용매를 더 포함하고 있어도 된다. 용매로서는, 예를 들어, 케톤류, 에테르류, 탄화수소류, 에스테르류, 물, 알코올류, 셀로솔브류, 셀로솔브아세테이트류, 술폭시드류, 아미드류 등을 예시할 수 있다. 또한, 용매는 혼합 용매여도 된다. 이들 용매 중, 케톤류(아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 시클로헥사논 등)를 포함하는 것이 바람직하고, 케톤류와 알코올류(에탄올, 이소프로판올, 부탄올, 시클로헥산올 등)의 혼합 용매가 특히 바람직하다. 용매의 비율은, 경화성 수지 100중량부에 대하여 예를 들어 30 내지 300중량부, 바람직하게는 50 내지 250중량부, 더욱 바람직하게는 100 내지 200중량부 정도이다.The curable composition before curing may further contain a solvent. Examples of the solvent include ketones, ethers, hydrocarbons, esters, water, alcohols, cellosolves, cellosolve acetates, sulfoxides, and amides. In addition, a mixed solvent may be sufficient as a solvent. Among these solvents, those containing ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) are preferred, and mixed solvents of ketones and alcohols (ethanol, isopropanol, butanol, cyclohexanol, etc.) are particularly preferred. desirable. The proportion of the solvent is, for example, 30 to 300 parts by weight, preferably 50 to 250 parts by weight, and more preferably about 100 to 200 parts by weight, based on 100 parts by weight of the curable resin.
단층 필름 및 저마찰층의 평균 두께는, 각각, 예를 들어 1 내지 30㎛, 바람직하게는 3 내지 20㎛, 더욱 바람직하게는 5 내지 15㎛(특히 8 내지 10㎛) 정도이다. 부언하면, 본 명세서 및 특허 청구 범위에 있어서, 단층 필름 및 저마찰층의 평균 두께는, 후술하는 실시예에 기재된 방법으로 측정할 수 있다.The average thickness of the single-layer film and the low-friction layer is, for example, about 1 to 30 μm, preferably about 3 to 20 μm, more preferably about 5 to 15 μm (particularly about 8 to 10 μm), respectively. Incidentally, in the present specification and claims, the average thickness of the single-layer film and the low-friction layer can be measured by the method described in Examples described later.
(적층체)(Laminate)
저마찰 필름이 적층체일 경우, 상기 저마찰층이 최표면에 배치되어 있으면 되고, 적층 구조는 특별히 한정되지 않지만, 생산성이나 취급성 등의 점에서, 기재층 상에 저마찰층이 적층되어 있는 구조(기재층과, 이 기재층의 한쪽 면에 적층된 저마찰층과의 적층체)가 바람직하다.When the low-friction film is a laminate, the low-friction layer may be disposed on the outermost surface, and the laminate structure is not particularly limited. From the viewpoint of productivity and handling, the low-friction layer is laminated on the substrate layer. (A laminated body of a base material layer and a low friction layer laminated on one side of the base material layer) is preferable.
기재층의 재질은 특별히 한정되지 않고 각종 유기 재료(열가소성 수지, 열경화성 수지, 광경화성 수지 등)나 무기 재료(유리, 세라믹스, 금속 등)로부터 선택할 수 있지만, 터치 패널 디스플레이 등의 광학 용도의 보호 필름으로서 이용되는 경우에는, 투명 재료가 바람직하다.The material of the substrate layer is not particularly limited and can be selected from various organic materials (thermoplastic resin, thermosetting resin, photocurable resin, etc.) and inorganic materials (glass, ceramics, metal, etc.), but a protective film for optical applications such as touch panel displays. When used as a transparent material, a transparent material is preferable.
투명 재료로서는, 예를 들어, 유리 등의 무기 재료; 셀룰로오스에스테르, 폴리에스테르, 폴리아미드, 폴리이미드, 폴리카르보네이트, (메트)아크릴계 중합체 등의 유기 재료 등을 들 수 있다. 이들 중, 셀룰로오스에스테르, 폴리에스테르 등이 범용된다.As a transparent material, For example, Inorganic materials, such as glass; and organic materials such as cellulose esters, polyesters, polyamides, polyimides, polycarbonates, and (meth)acrylic polymers. Among these, cellulose esters, polyesters and the like are generally used.
셀룰로오스에스테르로서는, 셀룰로오스트리아세테이트(TAC) 등의 셀룰로오스아세테이트, 셀룰로오스아세테이트프로피오네이트, 셀룰로오스아세테이트부티레이트 등의 셀룰로오스아세테이트 C3-4 아실레이트 등을 들 수 있다. 폴리에스테르로서는, 폴리에틸렌테레프탈레이트(PET), 폴리에틸렌나프탈레이트(PEN) 등의 폴리알킬렌아릴레이트 등을 들 수 있다.Examples of the cellulose ester include cellulose acetates such as cellulose triacetate (TAC), cellulose acetate C 3-4 acylates such as cellulose acetate propionate, and cellulose acetate butyrate. Examples of polyester include polyalkylene arylates such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).
이들 중, 기계적 특성이나 투명성 등의 밸런스가 우수한 점에서, PET나 PEN 등의 폴리 C2-4 알킬렌 C8-12 아릴레이트가 바람직하다.Among these, poly C 2-4 alkylene C 8-12 arylates such as PET and PEN are preferable from the viewpoint of excellent balance of mechanical properties and transparency.
폴리에스테르로 형성된 기재층은, 1축 또는 2축 연신 필름이어도 되지만, 저복굴절률이며, 광학적으로 등방성이 우수한 점에서, 미연신 필름이어도 된다.The base material layer formed of polyester may be a uniaxially or biaxially stretched film, but may also be an unstretched film from the viewpoint of low birefringence and excellent optical isotropy.
기재층은, 표면 처리(예를 들어, 코로나 방전 처리, 화염 처리, 플라스마 처리, 오존이나 자외선 조사 처리 등)되어 있어도 되고, 접착 용이층을 갖고 있어도 된다.The substrate layer may be subjected to surface treatment (for example, corona discharge treatment, flame treatment, plasma treatment, ozone or ultraviolet irradiation treatment, etc.) or may have an easy-adhesive layer.
기재층의 평균 두께는 10㎛ 이상이어도 되고, 예를 들어 12 내지 500㎛, 바람직하게는 20 내지 300㎛, 더욱 바람직하게는 30 내지 200㎛ 정도이다.The average thickness of the substrate layer may be 10 μm or more, for example, 12 to 500 μm, preferably 20 to 300 μm, and more preferably about 30 to 200 μm.
(점착층)(adhesive layer)
본 발명의 저마찰 필름은, 상기 범위의 Rku 및 Rt를 갖는 요철 구조가 형성된 표면의 이면(단층 필름에 있어서의 저마찰 필름의 이면이나, 기재층의 표면 등)의 적어도 일부에 점착층이 형성되어 있어도 된다. 상기 이면에 점착층을 형성한 저마찰 필름은, 스마트폰이나 태블릿 PC 등의 터치 패널 디스플레이에 있어서의 보호 필름으로서도 사용 가능하다.In the low-friction film of the present invention, an adhesive layer is formed on at least a part of the back surface (the back surface of the low-friction film in a single-layer film, the surface of the substrate layer, etc.) of the surface on which the uneven structure having Rku and Rt in the above range is formed it may be The low-friction film in which the adhesive layer is formed on the back surface can also be used as a protective film for touch panel displays such as smart phones and tablet PCs.
점착층은, 관용의 투명한 점착제로 형성되어 있다. 점착제로서는, 예를 들어, 고무계 점착제, 아크릴계 점착제, 올레핀계 점착제(변성 올레핀계 점착제 등), 실리콘계 점착제 등을 예시할 수 있다. 이들 점착제는, 단독으로 또는 2종 이상 조합하여 사용할 수 있다. 이들 점착제 중, 광학 특성이나 리워크성 등의 점에서, 실리콘계 점착제가 바람직하다.The adhesive layer is made of a commonly used transparent adhesive. Examples of the pressure-sensitive adhesive include rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, olefin-based pressure-sensitive adhesives (modified olefin-based pressure-sensitive adhesives, etc.), silicone pressure-sensitive adhesives, and the like. These adhesives can be used individually or in combination of 2 or more types. Among these pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives are preferable in terms of optical properties, reworkability, and the like.
점착층의 평균 두께는, 예를 들어 1 내지 150㎛, 바람직하게는 10 내지 100㎛, 더욱 바람직하게는 20 내지 70㎛(특히 25 내지 50㎛) 정도이다.The average thickness of the adhesive layer is, for example, about 1 to 150 μm, preferably about 10 to 100 μm, and more preferably about 20 to 70 μm (particularly about 25 to 50 μm).
점착층은, 이면 전체에 형성되어 있어도 되고, 이면의 일부(예를 들어, 주연부)에 형성하든 어느 것이어도 된다. 또한, 주연부에 형성하는 경우, 접착을 위한 취급성을 향상시킬 목적으로, 저마찰 필름의 주연부에 프레임상 부재(예를 들어, 주연부에 플라스틱 시트를 적층)를 형성하고, 프레임상 부재에 점착층을 형성해도 된다.The adhesive layer may be formed on the entire back surface or may be formed on a part of the back surface (for example, the periphery). In addition, in the case of forming on the periphery, for the purpose of improving the handleability for adhesion, a frame-like member (for example, a plastic sheet laminated on the periphery) is formed on the periphery of the low-friction film, and an adhesive layer is formed on the frame-like member. may form
[저마찰 필름의 제조 방법][Method for producing low-friction film]
본 발명의 저마찰 필름의 제조 방법은, 표면에 상기 범위의 Rku 및 Rt로 조정된 요철 구조를 형성할 수 있는 방법이면, 특별히 한정되지 않고 저마찰 필름의 재질에 따라서 적절히 선택할 수 있다. 구체적인 제조 방법으로서는, 예를 들어, 경화성 수지를 포함하는 경화성 조성물을 경화하는 경화 공정을 포함하는 방법(예를 들어, 미립자를 포함하는 경화성 조성물을, 미립자를 돌출시켜서 경화하는 방법, 상분리 가능한 수지 성분을 포함하는 경화성 조성물의 상기 수지 성분을 상분리시킨 후에 경화하는 방법 등), 표면에 요철 구조를 갖는 형을 사용하여 전사하는 방법, 절삭 가공에 의해 요철 구조를 형성하는 방법(예를 들어, 레이저 등을 이용한 절삭 가공 등), 연마에 의해 요철 구조를 형성하는 방법(예를 들어, 샌드블라스트법이나 비즈 샷법 등), 에칭에 의해 요철 구조를 형성하는 방법 등을 들 수 있다.The manufacturing method of the low-friction film of the present invention is not particularly limited as long as it is a method capable of forming a concavo-convex structure adjusted to Rku and Rt within the above ranges on the surface, and can be appropriately selected according to the material of the low-friction film. As a specific manufacturing method, for example, a method including a curing step of curing a curable composition containing curable resin (for example, a method of curing a curable composition containing fine particles by protruding fine particles, a resin component capable of phase separation) A method of curing after phase-separating the resin component of a curable composition comprising a), a method of transferring using a mold having a concavo-convex structure on the surface, a method of forming a concavo-convex structure by cutting (eg, laser, etc.) cutting, etc.), a method of forming a concave-convex structure by polishing (for example, a sandblasting method or a bead shot method, etc.), a method of forming a concavo-convex structure by etching, and the like.
이들 방법 중, 표면의 요철 구조가 상기 범위의 Rku 및 Rt로 조정된 저마찰 필름을 높은 생산성으로 제조할 수 있는 점에서, 경화성 수지를 포함하는 경화성 조성물을 경화하는 경화 공정을 포함하는 방법이 바람직하고, 예를 들어, 지지체(저마찰 필름이 적층체일 경우, 저마찰 필름을 포함하는 상기 기재층) 상에 액상의 경화성 조성물을 도포하여 건조한 후, 경화시키는 방법이어도 된다.Among these methods, a method including a curing step of curing a curable composition containing a curable resin is preferable from the viewpoint that a low-friction film having a surface concavo-convex structure adjusted to Rku and Rt within the above range can be produced with high productivity. Alternatively, for example, a method of applying a liquid curable composition onto a support (when the low-friction film is a laminate, the base material layer including the low-friction film), drying it, and then curing it may be used.
도포 방법으로서는, 관용의 방법, 예를 들어, 롤 코터, 에어 나이프 코터, 블레이드 코터, 로드 코터, 리버스 코터, 바 코터, 콤마 코터, 딥·스퀴즈 코터, 다이 코터, 그라비아 코터, 마이크로그라비아 코터, 실크스크린 코터 등의 코터법, 침지법, 스프레이법, 스피너법 등을 들 수 있다. 이들 방법 중, 바 코터법이나 그라비아 코터법 등이 범용된다. 부언하면, 필요한 경우, 도포액은 복수회에 걸쳐 도포해도 된다.As the coating method, a conventional method, for example, roll coater, air knife coater, blade coater, rod coater, reverse coater, bar coater, comma coater, dip squeeze coater, die coater, gravure coater, microgravure coater, silk A coater method, such as a screen coater, a dipping method, a spray method, a spinner method, etc. are mentioned. Among these methods, a bar coater method, a gravure coater method, and the like are generally used. Incidentally, if necessary, the coating liquid may be applied multiple times.
건조 온도는, 예를 들어 30 내지 120℃, 바람직하게는 50 내지 110℃, 더욱 바람직하게는 60 내지 100℃(특히 70 내지 90℃) 정도이다. 건조 시간은, 예를 들어 0.1 내지 10분, 바람직하게는 0.3 내지 5분, 더욱 바람직하게는 0.5 내지 3분 정도이다.The drying temperature is, for example, about 30 to 120°C, preferably about 50 to 110°C, more preferably about 60 to 100°C (particularly about 70 to 90°C). The drying time is, for example, about 0.1 to 10 minutes, preferably about 0.3 to 5 minutes, and more preferably about 0.5 to 3 minutes.
경화 방법은, 경화성 수지의 종류에 따라, 활성 광선(자외선, 전자선 등)이나 열 등을 부여하는 방법이면 되고, 광경화성 수지의 경우, 광 조사는, 광경화 수지 등의 종류에 따라 선택할 수 있고, 통상, 자외선, 전자선 등을 이용할 수 있다. 범용적인 노광원은, 통상, 자외선 조사 장치이다.The curing method may be a method of applying actinic rays (ultraviolet rays, electron beams, etc.) or heat depending on the type of curable resin, and in the case of photocurable resin, light irradiation can be selected according to the type of photocurable resin , usually, ultraviolet rays, electron beams, and the like can be used. A general-purpose exposure light source is usually an ultraviolet irradiation device.
광원으로서는, 예를 들어, 자외선의 경우에는, Deep UV 램프, 저압 수은 램프, 고압 수은 램프, 초고압 수은 램프, 할로겐 램프, 레이저 광원(헬륨-카드뮴 레이저, 엑시머 레이저 등의 광원) 등을 이용할 수 있다. 조사광량(조사 에너지)은 도막의 두께에 따라 상이하고, 예를 들어 10 내지 10000mJ/㎠, 바람직하게는 20 내지 5000mJ/㎠, 더욱 바람직하게는 30 내지 3000mJ/㎠ 정도이다. 광 조사는, 필요하면, 불활성 가스 분위기 중에서 행해도 된다.As the light source, for example, in the case of ultraviolet light, a deep UV lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, a laser light source (a light source such as a helium-cadmium laser or an excimer laser), etc. can be used. . The irradiation light amount (irradiation energy) differs depending on the thickness of the coating film, and is, for example, about 10 to 10000 mJ/cm 2 , preferably about 20 to 5000 mJ/cm 2 , and more preferably about 30 to 3000 mJ/cm 2 . Light irradiation may be performed in an inert gas atmosphere, if necessary.
이러한 경화성 조성물을 경화하는 방법에 있어서, 표면의 Rku 및 Rt가 상기 범위로 조정된 요철 구조를 형성하는 방법으로서는, 상기 경화성 조성물에 미립자를 배합하고, 미립자를 돌출시켜서 경화하는 방법(미립자를 이용하는 방법), 상기 경화성 조성물에 상분리 가능한 수지 성분을 배합하고, 이 수지 성분을 상분리시킨 후에 경화하는 방법(상분리를 이용하는 방법) 등을 들 수 있다.In a method of curing such a curable composition, as a method of forming a concavo-convex structure in which Rku and Rt of the surface are adjusted to the above ranges, fine particles are blended into the curable composition, and the curable composition is cured by protruding the fine particles (method using fine particles). ), a method of mixing a resin component capable of phase separation with the curable composition, and curing after phase separation of the resin component (method using phase separation), and the like.
미립자를 이용하는 방법에서는, 표면으로부터 미립자가 돌출된 상태에서, 경화성 조성물을 경화시킴으로써, 표면에 요철 구조를 형성해도 된다.In the method using the fine particles, the concavo-convex structure may be formed on the surface by curing the curable composition in a state where the fine particles protrude from the surface.
상분리를 이용하는 방법에서는, 상분리 가능한 수지 성분 및 용매를 포함하는 조성물의 액상으로부터, 용매를 건조 등에 의해 증발 또는 제거하는 과정에서, 조성물의 농축에 수반하여, 스피노달 분해(습식 스피노달 분해)에 의한 상분리가 발생하고, 상간 거리가 비교적 규칙적인 표면 요철 구조(상분리 구조)를 형성해도 된다. 상분리를 이용하는 방법으로서는, 예를 들어, 일본 특허 공개 제2007-187746, 일본 특허 공개 제2008-225195, 일본 특허 공개 제2009-267775, 일본 특허 공개 제2011-175601, 일본 특허 공개 제2014-85371호 공보에 기재된 방법 등도 이용할 수 있다. 상분리 가능한 수지 성분의 조합으로서는, 중합성기를 갖는 (메트)아크릴계 중합체와, 우레탄(메트)아크릴레이트와, 실리콘(메트)아크릴레이트와, 셀룰로오스에스테르의 조합이 바람직하다.In the method using phase separation, in the process of evaporating or removing the solvent from the liquid phase of a composition containing a resin component capable of phase separation and a solvent by drying or the like, in the process of concentrating the composition, spinodal decomposition (wet spinodal decomposition) Phase separation may occur and a surface concavo-convex structure (phase separation structure) having a relatively regular distance between phases may be formed. As a method using phase separation, for example, Japanese Patent Laid-Open Nos. 2007-187746, 2008-225195, 2009-267775, 2011-175601, and 2014-85371 The method described in the gazette, etc. can also be used. As a combination of the resin component capable of phase separation, a combination of a (meth)acrylic polymer having a polymerizable group, urethane (meth)acrylate, silicone (meth)acrylate, and cellulose ester is preferable.
실시예Example
이하에, 실시예에 기초하여 본 발명을 보다 상세하게 설명하지만, 본 발명은 이들 실시예에 의해 한정되는 것은 아니다. 실시예 및 비교예에서 사용한 원료는 이하와 같으며, 얻어진 저마찰 필름을 이하의 방법으로 평가하였다.The present invention will be described in more detail below based on examples, but the present invention is not limited by these examples. The raw materials used in Examples and Comparative Examples were as follows, and the obtained low-friction films were evaluated by the following method.
[원료][Raw material]
중합성기를 갖는 아크릴계 중합체 A: 다이셀·올넥스(주)제 「KRM8713B」Acrylic polymer A having a polymerizable group: "KRM8713B" manufactured by Daicel Allnex Co., Ltd.
중합성기를 갖는 아크릴계 중합체 B: 다이셀·올넥스(주)제 「사이클로머 P」Acrylic polymer B having a polymerizable group: "Cyclomer P" manufactured by Daicel Allnex Co., Ltd.
아크릴계 중합체: 다이세이 파인케미컬(주)제 「8KX-078」Acrylic polymer: "8KX-078" manufactured by Daisei Fine Chemical Co., Ltd.
우레탄 변성 공중합 폴리에스테르 수지: 도요보(주)제 「바이런(등록 상표) UR-3200」Urethane-modified co-polyester resin: Toyobo Co., Ltd. "Byron (registered trademark) UR-3200"
셀룰로오스아세테이트프로피오네이트: 이스트만사제 「CAP-482-20」, 아세틸화도=2.5%, 프로피오닐화도=46%, 폴리스티렌 환산 수 평균 분자량 75000Cellulose acetate propionate: "CAP-482-20" manufactured by Eastman Co., Ltd., degree of acetylation = 2.5%, degree of propionylation = 46%, polystyrene conversion number average molecular weight 75000
우레탄아크릴레이트: 신나까무라 가가꾸 고교(주)제 「UA-53H」Urethane acrylate: "UA-53H" manufactured by Shin Nakamura Chemical Industry Co., Ltd.
실리콘아크릴레이트: 다이셀·올넥스(주)제 「EBECRYL1360」Silicone acrylate: "EBECRYL1360" manufactured by Daicel Allnex Co., Ltd.
PMMA 비즈 A: 세끼스이 가가꾸 고교(주)제 「SSX-115」, 평균 입경 15㎛PMMA beads A: Sekisui Chemical Kogyo Co., Ltd. "SSX-115", average particle diameter 15 μm
PMMA 비즈 B: 세끼스이 가가꾸 고교(주)제 「SSX-110」, 평균 입경 10㎛PMMA beads B: Sekisui Chemical Kogyo Co., Ltd. "SSX-110", average particle diameter 10 μm
나노실리카 함유 아크릴계 자외선(UV) 경화성 화합물: JSR(주)제 「Z7501」Nano-silica-containing acrylic ultraviolet (UV) curable compound: "Z7501" manufactured by JSR Co., Ltd.
광 개시제 A: BASF 재팬(주)제 「이르가큐어184」Photoinitiator A: BASF Japan Co., Ltd. "Irgacure 184"
광 개시제 B: BASF 재팬(주)제 「이르가큐어907」Photoinitiator B: BASF Japan Co., Ltd. "Irgacure 907"
폴리에틸렌테레프탈레이트(PET) 필름: 미쓰비시 쥬시(주)제 「다이어포일」.Polyethylene terephthalate (PET) film: Mitsubishi Jushi Co., Ltd. product "diaphragm".
[저마찰층의 두께][Thickness of low friction layer]
광학식 막 두께 측정기를 사용하여, 임의의 10군데를 측정하고, 평균값을 산출하였다.Using an optical film thickness meter, 10 arbitrary locations were measured, and an average value was calculated.
[표면 형상][Surface shape]
JIS B0601에 준거하여, 광학식 표면 조도계((주)히타치 하이테크 사이언스제 「바트 스캔 R5500G」)를 사용하여, 주사 범위 2.5㎜ 사방, 주사 횟수 2회의 조건에서, 최대 단면 높이(Rt) 및 요철의 첨도(Rku)를 측정하였다.Based on JIS B0601, using an optical surface roughness meter (“Bart Scan R5500G” manufactured by Hitachi High-Tech Science Co., Ltd.), the maximum cross-sectional height (Rt) and the kurtosis of irregularities were measured under the conditions of a scanning range of 2.5 mm square and a scanning frequency of 2 times. (Rku) was measured.
[동마찰 계수 및 상대 동마찰 계수][Coefficient of dynamic friction and coefficient of relative dynamic friction]
정동 마찰 측정기((주)트리니티 랩제 「핸디 트라이보마스터 TL201Ts」)를 사용하여, 측정 조건(하중 20g중, 속도 25㎜/초)에서 동마찰력(동마찰 계수)을 측정하였다. 접촉자로서는, 5㎜ 두께의 스펀지 시트(세메다인사제 「간극용 테이프 N-1」)에 인공 피부(뷰랙스사제 「바이오스킨」)를 첩부한 접촉자를 사용하였다. 상대 동마찰 계수는, 측정 대상인 필름의 동마찰력을, 유리(소다석회 유리)를 검체로 하여 측정한 동마찰력으로 나눔으로써 구하였다.The dynamic friction force (coefficient of dynamic friction) was measured using a static friction measuring instrument (“Handy Tribomaster TL201Ts” manufactured by Trinity Lab Co., Ltd.) under measurement conditions (load of 20 g, speed of 25 mm/sec). As the contact, a contact was used in which artificial skin ("Bio Skin" manufactured by Viewrax) was affixed to a 5 mm thick sponge sheet ("Gap Tape N-1" manufactured by Semedin Corporation). The relative kinetic friction coefficient was obtained by dividing the kinetic friction force of the film to be measured by the kinetic friction force measured using glass (soda lime glass) as a sample.
[손가락 미끄럼성][Finger slipperiness]
손가락 미끄럼성의 평가는, 25㎛ 두께의 옵티컬 클리어 어드히시브(OCA) 필름을 사용하여, 얻어진 저마찰 필름의 기재층측을 아크릴판에 첩부한 것을 준비하고, 스마트폰을 조작하는 감각으로 필름상(저마찰층의 표면)을 집게 손가락을 슬라이드시킴으로써 행하였다. 20명의 피험자에 대하여 하기 5단계의 기준으로 평가 결과를 청취하였다.To evaluate the finger slipperiness, a 25 μm thick optical clear adhesive (OCA) film was prepared by attaching the base layer side of the obtained low-friction film to an acrylic plate, and the film-like ( surface of the low-friction layer) was performed by sliding the index finger. About 20 subjects, the evaluation results were listened to based on the following 5 steps.
1점: 손가락이 미끄러지기 어렵고, 조작의 도중에도 걸린다1 point: Fingers are hard to slip and get caught in the middle of operation
2점: 미끄럼 초기에 걸림이 있고, 미끄러지기 시작한 후의 마찰감이 크다2 points: There is a snag at the beginning of sliding, and the friction after starting to slide is great
3점: 미끄럼 초기에 걸림이 있고, 미끄러지기 시작한 후의 마찰감은 작다3 points: There is a catch at the beginning of sliding, and the friction after starting to slide is small
4점: 미끄럼 초기에 조금 걸림이 있지만, 조작 중에는 마찰감을 느끼지 않는다4 points: There is a little snag at the beginning of sliding, but no friction is felt during operation.
5점: 미끄럼 초기에 걸림이 없고, 조작 중에 마찰감을 느끼지 않는다.5 points: There is no snag at the beginning of sliding, and no feeling of friction is felt during operation.
실시예 1Example 1
중합성기를 갖는 아크릴계 중합체 A 216중량부, PMMA 비즈 A 1중량부, 광 개시제 A 1중량부, 광 개시제 B 1중량부를, 메틸에틸케톤 117중량부에 용해하였다. 이 용액을, 와이어 바 #14를 사용하여, PET 필름 상에 유연한 후, 100℃의 오븐 내에서 1분간 방치하고, 용매를 증발시켜서 두께 약 12㎛의 저마찰층을 형성시켰다. 그리고, 저마찰층에, 고압 수은 램프로부터의 자외선을 약 5초간 조사해서(적산 광량 약 100mJ/㎠ 조사) UV 경화 처리하여, 저마찰 필름을 얻었다.216 parts by weight of acrylic polymer A having a polymerizable group, 1 part by weight of PMMA beads A, 1 part by weight of photoinitiator A, and 1 part by weight of photoinitiator B were dissolved in 117 parts by weight of methyl ethyl ketone. After this solution was cast on a PET film using a wire bar #14, it was allowed to stand in an oven at 100°C for 1 minute, and the solvent was evaporated to form a low-friction layer having a thickness of about 12 µm. Then, the low-friction layer was irradiated with ultraviolet rays from a high-pressure mercury lamp for about 5 seconds (irradiation at a cumulative light amount of about 100 mJ/cm 2 ) to carry out a UV curing treatment to obtain a low-friction film.
실시예 2Example 2
중합성기를 갖는 아크릴계 중합체 B 50중량부, 셀룰로오스아세테이트프로피오네이트 4중량부, 우레탄아크릴레이트 76중량부, 실리콘아크릴레이트 1중량부, 광 개시제 A 1중량부, 광 개시제 B 1중량부를, 메틸에틸케톤 176중량부와 1-부탄올 28중량부의 혼합 용매에 용해하였다. 이 용액을, 와이어 바 #18을 사용하여, PET 필름 상에 유연한 후, 80℃의 오븐 내에서 1분간 방치하고, 용매를 증발시켜서 두께 약 9㎛의 저마찰층을 형성시켰다. 그리고, 저마찰층에, 고압 수은 램프로부터의 자외선을 약 5초간 조사(적산 광량 약 100mJ/㎠ 조사)하여 UV 경화 처리하여, 저마찰 필름을 얻었다.50 parts by weight of acrylic polymer B having a polymerizable group, 4 parts by weight of cellulose acetate propionate, 76 parts by weight of urethane acrylate, 1 part by weight of silicone acrylate, 1 part by weight of photoinitiator A, 1 part by weight of photoinitiator B, methylethyl It was dissolved in a mixed solvent of 176 parts by weight of ketone and 28 parts by weight of 1-butanol. After this solution was cast on a PET film using a wire bar #18, it was allowed to stand in an oven at 80° C. for 1 minute, and the solvent was evaporated to form a low friction layer having a thickness of about 9 μm. Then, the low-friction layer was irradiated with ultraviolet rays from a high-pressure mercury lamp for about 5 seconds (irradiation at a cumulative amount of light of about 100 mJ/cm 2 ) to carry out a UV curing treatment to obtain a low-friction film.
비교예 1Comparative Example 1
중합성기를 갖는 아크릴계 중합체 A 216중량부, PMMA 비즈 B 1중량부, 광 개시제 A 1중량부, 광 개시제 B 1중량부를, 메틸에틸케톤 117중량부에 용해하였다. 이 용액을, 와이어 바 #14를 사용하여, PET 필름 상에 유연한 후, 100℃의 오븐 내에서 1분간 방치하고, 용매를 증발시켜서 두께 약 8㎛의 저마찰층을 형성시켰다. 그리고, 저마찰층에, 고압 수은 램프로부터의 자외선을 약 5초간 조사(적산 광량 약 100mJ/㎠ 조사)하여 UV 경화 처리하여, 저마찰 필름을 얻었다.216 parts by weight of acrylic polymer A having a polymerizable group, 1 part by weight of PMMA beads B, 1 part by weight of photoinitiator A, and 1 part by weight of photoinitiator B were dissolved in 117 parts by weight of methyl ethyl ketone. After this solution was cast on a PET film using a wire bar #14, it was allowed to stand in an oven at 100°C for 1 minute, and the solvent was evaporated to form a low-friction layer having a thickness of about 8 µm. Then, the low-friction layer was irradiated with ultraviolet rays from a high-pressure mercury lamp for about 5 seconds (irradiation at a cumulative amount of light of about 100 mJ/cm 2 ) to carry out a UV curing treatment to obtain a low-friction film.
비교예 2Comparative Example 2
아크릴계 중합체 34.2중량부, 우레탄 변성 공중합 폴리에스테르 수지 20중량부, 나노실리카 함유 아크릴계 UV 경화성 화합물 166.3중량부, 실리콘아크릴레이트 0.2중량부, 광 개시제 A 1중량부, 광 개시제 B 1중량부를, 메틸에틸케톤 179중량부에 용해하였다. 이 용액을, 와이어 바 #16을 사용하여, PET 필름 상에 유연한 후, 80℃의 오븐 내에서 1분간 방치하고, 용매를 증발시켜서 두께 약 5㎛의 저마찰층을 형성시켰다. 그리고, 저마찰층에, 고압 수은 램프로부터의 자외선을 약 5초간 조사(적산 광량 약 100mJ/㎠ 조사)하여 UV 경화 처리하여, 저마찰 필름을 얻었다.34.2 parts by weight of acrylic polymer, 20 parts by weight of urethane-modified co-polyester resin, 166.3 parts by weight of nano-silica-containing acrylic UV curable compound, 0.2 part by weight of silicone acrylate, 1 part by weight of photoinitiator A, 1 part by weight of photoinitiator B, methylethyl Dissolved in 179 parts by weight of ketones. After this solution was cast on a PET film using a wire bar #16, it was allowed to stand in an oven at 80° C. for 1 minute, and the solvent was evaporated to form a low-friction layer having a thickness of about 5 μm. Then, the low-friction layer was irradiated with ultraviolet rays from a high-pressure mercury lamp for about 5 seconds (irradiation at a cumulative amount of light of about 100 mJ/cm 2 ) to carry out a UV curing treatment to obtain a low-friction film.
비교예 3Comparative Example 3
시판하고 있는 스마트폰용 보호 시트인 PM-A15FLGM(ELECOM사제)은 패키지에 「궁극의 손가락 미끄럼 필름」이나 「슈퍼 스무스 필름」이라고 명문화되어 있기 때문에, 손가락 미끄럼이 좋은 필름의 비교예로서 채용하였다.PM-A15FLGM (manufactured by ELECOM), a commercially available smartphone protection sheet, is clearly labeled as "ultimate finger-slip film" or "super smooth film" on the package, so it was used as a comparative example of a film with good finger-slip.
비교예 4Comparative Example 4
시판하고 있는 스마트폰용 보호 시트인 PM-A15FLST(ELECOM사제)도 패키지에 「손가락 미끄럼 미끌미끌」이나 「슈퍼 스무스 필름」이라고 명문화되어 있기 때문에, 손가락 미끄럼이 좋은 필름의 비교예로서 채용하였다.PM-A15FLST (manufactured by ELECOM), a commercially available protective sheet for smartphones, is also described as "finger slippery" or "super smooth film" on the package, so it was adopted as a comparative example of a film with good finger slippage.
실시예 및 비교예에서 얻어진 저마찰 필름의 특성을 평가한 결과를 표 1에 나타내었다.Table 1 shows the results of evaluating the properties of the low-friction films obtained in Examples and Comparative Examples.
표 1의 결과로부터 명백해진 바와 같이, 실시예의 저마찰 필름은, 동마찰 계수 및 상대 동마찰 계수가 낮고 손가락 미끄럼성이 우수하다. 한편, 비교예 1, 3, 4와 같이 첨도만 높은 값이면 손가락 미끄럼성은 높아지지 않는다. 또한 비교예 2와 같이 최대 단면 높이만 높아도 실시예보다 손가락 미끄럼성이 떨어진다.As is clear from the results of Table 1, the low-friction films of Examples have low coefficients of kinetic friction and relative kinetic friction coefficients, and are excellent in finger slipperiness. On the other hand, when only the kurtosis has a high value as in Comparative Examples 1, 3, and 4, the finger slipperiness does not increase. In addition, as in Comparative Example 2, even if only the maximum cross-sectional height is high, the finger slipperiness is inferior to that of Example 2.
본 발명의 저마찰 필름은, 퍼스널 컴퓨터(태블릿 PC 등)나 스마트폰 등에 있어서의 터치 패널 디스플레이, 가전 제품의 하우징, 건축 재료 등의 각종 성형체의 표면을 커버하기 위한 표면 보호 또는 커버 필름으로서 이용할 수 있고, 특히, 손으로 접촉하여 조작하는 개소에 저마찰성을 부여함으로써 닿는 느낌을 높이는 필름으로서 유용하다.The low-friction film of the present invention can be used as a surface protection or cover film for covering the surfaces of various molded bodies such as touch panel displays in personal computers (tablet PCs, etc.) and smartphones, housings of household appliances, and building materials. In particular, it is useful as a film that enhances the feeling of touch by imparting low friction to the area touched and operated by hand.
Claims (12)
상기 경화성 수지가, 중합성기를 갖는 (메트)아크릴계 중합체를 포함하는 필름. It is formed of a cured product of a curable composition containing a curable resin, and includes a low friction layer disposed on an outermost layer, and the surface of the low friction layer has a kurtosis (Rku) of 2 or more and a maximum cross-sectional height (Rt) of 1 μm or more ), and a film having an adhesive layer formed on at least a part of the back surface with respect to the surface,
The film in which the said curable resin contains the (meth)acrylic-type polymer which has a polymeric group.
상기 경화성 수지가, 중합성기를 갖는 (메트)아크릴계 중합체를 포함하는 방법.The surface of the low-friction layer of a film formed of a cured product of a curable composition containing a curable resin and including a low-friction layer disposed on the outermost layer has a kurtosis (Rku) of 2 or more and a maximum cross-sectional height (Rt) of 1 μm or more ), thereby improving the finger slipperiness of the film having an adhesive layer formed on at least a part of the back surface with respect to the surface,
The method in which the said curable resin contains the (meth)acrylic-type polymer which has a polymeric group.
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KR1020227008701A KR102500023B1 (en) | 2017-10-25 | 2018-10-11 | Low-friction film, manufacturing method therefor, molded body, and method for enhancing finger slipperiness |
KR1020237004882A KR102600830B1 (en) | 2017-10-25 | 2018-10-11 | Low-friction film, manufacturing method therefor, molded body, and method for enhancing finger slipperiness |
KR1020207008182A KR102377190B1 (en) | 2017-10-25 | 2018-10-11 | Low friction film and manufacturing method thereof, molded article and method for improving finger slipperiness |
KR1020227008702A KR102500025B1 (en) | 2017-10-25 | 2018-10-11 | Low-friction film, manufacturing method therefor, molded body, and method for enhancing finger slipperiness |
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US (1) | US20200247965A1 (en) |
JP (1) | JPWO2019082663A1 (en) |
KR (5) | KR102500023B1 (en) |
CN (2) | CN111051399B (en) |
TW (2) | TWI795452B (en) |
WO (1) | WO2019082663A1 (en) |
Families Citing this family (2)
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EP3978556A4 (en) * | 2019-05-31 | 2023-09-20 | Mitsui Chemicals Tohcello, Inc. | Packaging film, package, and method for producing laminated film |
WO2020255200A1 (en) * | 2019-06-17 | 2020-12-24 | リンテック株式会社 | Display protective film |
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WO2008038714A1 (en) | 2006-09-29 | 2008-04-03 | Dai Nippon Printing Co., Ltd. | Optically functional film |
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JP2015052025A (en) * | 2013-09-05 | 2015-03-19 | 三菱樹脂株式会社 | Resin film and decorative sheet |
JP2016018068A (en) * | 2014-07-08 | 2016-02-01 | 旭硝子株式会社 | Substrate with anti-glare film, and articles having the same |
KR20160138436A (en) * | 2014-03-31 | 2016-12-05 | 주식회사 다이셀 | Transparent laminated film for pen input device and manufacturing method thereof |
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JP2009151476A (en) * | 2007-12-19 | 2009-07-09 | Nof Corp | Surface material for pen input device, and pen input device having the same |
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JP5501800B2 (en) * | 2010-02-25 | 2014-05-28 | 株式会社ダイセル | Transparent conductive film and touch panel |
JP6190581B2 (en) * | 2012-10-19 | 2017-08-30 | 株式会社ダイセル | Antiglare film and method for producing the same |
JP6222559B2 (en) * | 2012-11-08 | 2017-11-01 | 日油株式会社 | Urethane (meth) acrylate mixture and urethane (meth) acrylate composition |
JP2015034955A (en) * | 2013-08-09 | 2015-02-19 | 大日本印刷株式会社 | Transparent conductive laminate, touch panel, and touch panel intermediate laminate |
CN104915050B (en) * | 2014-03-11 | 2017-11-21 | 大日本印刷株式会社 | The manufacture method of the screening technique and optical sheet of touch panel, display device and optical sheet and optical sheet |
JP6619955B2 (en) * | 2015-06-17 | 2019-12-11 | 株式会社ダイセル | Wound healing film |
JP2017109350A (en) * | 2015-12-15 | 2017-06-22 | 大日本印刷株式会社 | Optical laminate |
JP6288228B2 (en) * | 2016-12-05 | 2018-03-07 | 大日本印刷株式会社 | Optical laminate, polarizing plate, and image display device |
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2018
- 2018-10-11 WO PCT/JP2018/037831 patent/WO2019082663A1/en active Application Filing
- 2018-10-11 JP JP2019550976A patent/JPWO2019082663A1/en active Pending
- 2018-10-11 KR KR1020227008701A patent/KR102500023B1/en active IP Right Grant
- 2018-10-11 KR KR1020237004882A patent/KR102600830B1/en active IP Right Grant
- 2018-10-11 KR KR1020207008182A patent/KR102377190B1/en active IP Right Grant
- 2018-10-11 KR KR1020227008702A patent/KR102500025B1/en active IP Right Grant
- 2018-10-11 CN CN201880052370.6A patent/CN111051399B/en active Active
- 2018-10-11 KR KR1020237004881A patent/KR102600827B1/en active IP Right Grant
- 2018-10-11 US US16/629,406 patent/US20200247965A1/en not_active Abandoned
- 2018-10-11 CN CN202310161186.8A patent/CN116284927A/en active Pending
- 2018-10-23 TW TW107137310A patent/TWI795452B/en active
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JP2007264281A (en) | 2006-03-28 | 2007-10-11 | Dainippon Printing Co Ltd | Hard coat layer provided with antifouling property |
WO2008038714A1 (en) | 2006-09-29 | 2008-04-03 | Dai Nippon Printing Co., Ltd. | Optically functional film |
KR20090077767A (en) * | 2006-10-06 | 2009-07-15 | 도레이 카부시키가이샤 | Hard-coating film, process for producing the same, and antireflection film |
JP2015052025A (en) * | 2013-09-05 | 2015-03-19 | 三菱樹脂株式会社 | Resin film and decorative sheet |
KR20160138436A (en) * | 2014-03-31 | 2016-12-05 | 주식회사 다이셀 | Transparent laminated film for pen input device and manufacturing method thereof |
JP2016018068A (en) * | 2014-07-08 | 2016-02-01 | 旭硝子株式会社 | Substrate with anti-glare film, and articles having the same |
Also Published As
Publication number | Publication date |
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KR102500023B1 (en) | 2023-02-16 |
KR20220039828A (en) | 2022-03-29 |
KR102600830B1 (en) | 2023-11-10 |
TWI795452B (en) | 2023-03-11 |
TW201922494A (en) | 2019-06-16 |
KR20230026532A (en) | 2023-02-24 |
WO2019082663A1 (en) | 2019-05-02 |
KR102600827B1 (en) | 2023-11-10 |
TW202333952A (en) | 2023-09-01 |
CN111051399A (en) | 2020-04-21 |
KR20200044058A (en) | 2020-04-28 |
KR102500025B1 (en) | 2023-02-16 |
US20200247965A1 (en) | 2020-08-06 |
JPWO2019082663A1 (en) | 2020-04-02 |
KR102377190B1 (en) | 2022-03-22 |
CN116284927A (en) | 2023-06-23 |
KR20220039829A (en) | 2022-03-29 |
CN111051399B (en) | 2023-02-17 |
TWI843462B (en) | 2024-05-21 |
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